U.S. patent number 3,979,331 [Application Number 05/530,092] was granted by the patent office on 1976-09-07 for catalyst for alkylating aromatic hydrocarbons.
This patent grant is currently assigned to NL Industries, Inc.. Invention is credited to George E. Stridde.
United States Patent |
3,979,331 |
Stridde |
* September 7, 1976 |
**Please see images for:
( Certificate of Correction ) ** |
Catalyst for alkylating aromatic hydrocarbons
Abstract
Alkylatable aromatic hydrocarbons are alkylated with olefins and
alkylhalides under anhydrous alkylating conditions in the presence
of certain metallic cation exchanged synthetic hectorite-type
catalysts in which the metallic cation has a Pauling
electronegativity greater than 1.0 and in which the central
octahedral layer contains one or more divalent metals which have an
ionic radius not greater than 0.75 A. In a specific embodiment,
1-dodecene is reacted with benzene by contacting the dodecene and
benzene under anhydrous alkylating conditions in the liquid phase
at the boiling point of the mixture with a catalyst comprising a
metallic cation such as Al.sup.3.sup.-, In.sup.3.sup.- and
Cr.sup.3.sup.- exchanged onto the surface of a synthetic
nickeliferous hectorite.
Inventors: |
Stridde; George E. (Houston,
TX) |
Assignee: |
NL Industries, Inc. (New York,
NY)
|
[*] Notice: |
The portion of the term of this patent
subsequent to June 22, 1992 has been disclaimed. |
Family
ID: |
27054687 |
Appl.
No.: |
05/530,092 |
Filed: |
December 6, 1974 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
503985 |
Sep 6, 1974 |
|
|
|
|
Current U.S.
Class: |
502/61; 502/74;
585/468; 502/73; 502/84 |
Current CPC
Class: |
B01J
21/16 (20130101); B01J 29/049 (20130101); C07C
2/66 (20130101); C07C 2/862 (20130101); C07C
2/66 (20130101); C07C 15/107 (20130101); C07C
2/66 (20130101); C07C 15/02 (20130101); C07C
2/862 (20130101); C07C 15/02 (20130101); B01J
2229/42 (20130101) |
Current International
Class: |
C07C
2/00 (20060101); B01J 21/00 (20060101); B01J
21/16 (20060101); B01J 29/00 (20060101); B01J
29/04 (20060101); C07C 2/66 (20060101); C07C
2/86 (20060101); B01J 027/06 (); B01J 029/00 ();
B01J 029/06 () |
Field of
Search: |
;252/455R,457,459,454,441 ;260/671R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dees; Carl F.
Attorney, Agent or Firm: House; Roy F. Larsen; Delmar H.
Lehman; Robert L.
Parent Case Text
This application is a continuation-in-part of my commonly owned
co-pending patent application Ser. No. 503,985 filed Sept. 6, 1974
entitled Process For Alkylating Aromatic Hydrocarbons And Catalyst
Therefor.
Claims
I claim:
1. A catalyst comprising a synthetic hectorite-type clay containing
a metallic cation having a Pauling electronegativity greater than
1.0 in cation exchange positions on the surface of said clay, said
catalyst having the following structural formula:
where
M is one or more divalent cations having an ionic radius not
greater than 0.75 A, provided that M is less than 95 mole percent
Mg, and
R is at least one of said metallic cations having a Pauling
electronegativity greater than 1.0 of valence z.
2. The catalyst of claim 1 wherein 0 .ltoreq. y .ltoreq. 2 and
wherein M is a divalent cation selected from the group consisting
of Mg, Ni, Co, and mixtures thereof.
3. The catalyst of claim 2 wherein M is less than 90 mole percent
Mg.
4. The catalyst of claim 3 wherein said R is selected from the
group consisting of Al.sup.3.sup.+, Cr.sup.3.sup.+, Ga.sup.3.sup.+,
In.sup.3.sup.+, Mn.sup.2.sup.+, Fe.sup.3.sup.+, Co.sup.3.sup.+,
Co.sup.2.sup.+, Ni.sup.2.sup.+, Cu.sup.2.sup.+, Ag.sup.+,
Be.sup.2.sup.+, La.sup.3.sup.+, Ce.sup.3.sup.+, Pd.sup.2.sup.+,
Pt.sup.2.sup.+, and mixtures thereof.
5. The catalyst of claim 3 wherein R is Al.sup. 3.sup.+.
Description
This invention relates to a process for the liquid phase alkylation
of aromatic hydrocarbons in which the catalyst comprises certain
cation-exchanged synthetic hectorite-type clays. More particularly,
the present invention is concerned with a method wherein an
aromatic hydrocarbon, e.g. benzene, and an alkylating agent, e.g.
an olefin, are reacted in the liquid phase in the presence of a
catalyst which comprises a synthetic hectorite-type mineral which
has a metal cation having a Pauling electronegativity greater than
1.0 in ion-exchange positions on the surface of the clay particles,
and in which the central octahedral layer contains one or more
divalent metals having an ionic radius not greater than 0.75 A as
more particularly described hereinafter. Alkylated aromatic
hydrocarbons have many uses dependng on their molecular weight and
structure. Thus low molecular weight alkylbenzenes are useful in
high octane gasolines and high molecular weight alkylbenzenes are
useful as intermediates in the production of a alkylbenzene
sulfonate detergents.
It has been reported that various materials containing acidic
catalytic sites are useful in catalyzing the reaction between
aromatic hydrocarbons and various alkylating agents such as olefins
and alkyl halides. See for example: The Kirt-Othmer Encyclopedia of
Chemical Technology, 2nd Edition, Vol. 1, pp. 882-901 (1963);
"Alkylation of Benzene with Dodecene-1 Catalyzed by Supported
Silicotungstic Acid," R. T. Sebulsky and A. M. Henke, Ind. Eng.
Chem. Process Res. Develop., Vol. 10, No. 2, 1971, pp. 272-279;
"Organic Molecule and Zeolite Crystal: At the Interface," P.B.
Venuto, Chem. Tech., April, 1971, pp. 215-224; "Catalysis by Metal
Halides, IV. Relative Efficiencies of Friedel-Crafts Catalysts in
Cyclohexane-Methylcyclopentane Isomerization, Alkylation of Benzene
and Polymerization of Styrene", G. A. Russell, J. Am. Chem. Soc.,
Vol. 81, 1959, pp. 4834-4838.
It has also been proposed to use various modified clays as
catalysts in various acid catalyzed reactions such as alkylation,
and the like. See for example the following U.S. Pat. Nos.
3,665,778; 3,665,780; 3,365,347; 2,392,945; 2,555,370; 2,582,956;
2,930,820; 3,360,573; 2,945,072; 3,074,983. The latter patent is
the only patent known to me which discloses the use of hectorite
clay as a catalyst. Other references which disclose the use of
clays as catalysts are as follows: "Acid Activation of Some
Bentonite Clays", G. A. Mills, J. Holmes and E. B. Cornelius, J.
Phy & Coll. Chem., Vol. 54, pp. 1170-1185 (1950); "H-Ion
Catalysis by Clays", N. T. Coleman and C. McAuliffe, Clays and Clay
Minerals, Vol. 4, pp. 282-289 (1955); "Clay Minerals as Catalysts:,
R. H. S. Robertson, Clay Minerals Bull., Vol. 1, No. 2, pp. 47-54
(1948); "Catalytic Decomposition of Glycerol by Layer Silicates",
G. F. Walker, Clay Minerals, Vol. 7, pp. 111-112 (1967); "Styrene
Polymerization with Cation-Exchanged Alumino-silicates", T.A.
Kusnitsyna and V. M Brmolko, Vysokomol. Soedin, Ser. B1968, Vol.
10, No. 10, pp. 776-9-- see Chem Abstracts 70:20373x (1969);
"Reactions Catalyzed by Minerals". Part I. Polymerization of
Styrene:, D. H. Solomon and M. J. Rosser, J. Applied Polymer
Science, Vol. 9, 1261-1271 (1965).
The structure of hectorite-type minerals is well known. See for
example the following publications, incorporated herein by
reference: "Clay Mineralogy", R. E. Grim, Chapter 4, 2nd Edition
(1968). McGraw-Hill Book Co.; "Rock-Forming Minerals". Vol. 3.
Sheet Silicates:, W. A. Deer, R. A. Howie, and J. Zussman, 226-245
(1962). John Wiley and Sons, Inc. The following references
incorporated here-in by reference, describe processes for the
hydrothermal synthesis of smectite-type minerals: "A Study of the
Synthesis of Hectorite", W.T. Granquist and S. S. Pollack. Clays
and Clay Minerals, Proc. Nat'l. Conf. Clays Clay Minerals.
8,150-169 (1960); "Synthesis of a Nickel-Containing
Montmorillonite", B. Siffert and F. Dennefeld.Comptes Rendus Acad.
Sci., Paris, Ser. D. 1968, 267 (20), 1545-8 (Reference Chemical
Abstracts, Vol. 70; 43448q); "Synthesis of Clay Minerals", S.
Caillere, S. Henin, and J. Esquivin. Bull. groupe franc. argiles.
9, No. 4, 67-76 (1957) (Reference Chemical Abstracts 55: 8190e);
U.S. Pat. No. 3,586,478; U.S. Pat. No. 3,666,407; U.S. Pat. No.
3,671,190; "Synthesis of Zinciferous Montmorillonite":, J.
Esquevin. Comptes Rendus, Acd. Sci., Paris, 241, 1485-6 (1955);
"Synthesis of Clay Minerals at Low Temperatures":, S. Henin. Natl.
Acad. Sci.- Natl. Research Council Publ. No. 456, 54-60 (1956);
"Synthesis of Nickel Hydrosilicates", P. Franzen and J. J. B. van
Eijk van Voorthuysen. Trans. 4th Int. Congress Soil Sci., Amsterdam
3:34-7, 4:64 (1950).
I have now found that certain synthetic trioctahedral 2:1
layer-lattice smectite-type minerals, particularly certain
synthetic hectorite-type minerals, which have had their
exchangeable cations replaced with a metallic cation having a
Pauling electronegativity greater than 1.0 are effective catalysts
for the alkylation of alkylatable aromatic hydrocarbons, e.g.
benzene, with an olefin or alkyl halide under anhydrous alkylating
conditions in the liquid phase.
Accordingly, it is an object of this invention to provide a process
for alkylating in the liquid phase an alkylatable aromatic
hydrocarbon with an olefin or alkyl halide under anhydrous
alkylating conditions in the presence of certain synthetic
hectorite-type catalysts in which the central octahedral layer
contains one or more divalent metals having an ionic radius not
greater than 0.75 A and which has in its cation exchange positions
a metallic cation having a Pauling electronegativity greater than
1.0. It is another object of this invention to provide a method of
alkylating aromatic hydrocarbons which comprises contacting in the
liquid phase an alkylatable aromatic hydrocarbon with an olefin or
alkyl halide in a reaction zone which is substantially free of
water and in the presence of an effective amount of a catalyst,
said catalyst comprising certain metallic cation exchanged
synthetic hectorite-type clays wherein the metallic cation has a
Pauling electronegativity greater than 1.0 and in which the central
octahedral layer contains one or more divalent metals having an
ionic radius not greater than 0.75 A. Another object is to provide
a new catalyst which comprises a metallic cation exchanged
synthetic hectorite-like clay in which the central octahedral layer
contains one or more divalent metals having an ionic radius not
greater than 0.75 A, provided that said octahedral layer contains
less than 95 mole percent Mg, wherein the metallic cation has a
Pauling electronegativity greater than 1.0. Other objects and
advantages of this invention will become apparent to those skilled
in the art upon reading the disclosure and the appended claims.
The catalyst of this invention comprises (1) a metallic cation
which has a Pauling electronegativity greater than 1.0 exchanged
onto the surface of (2) certain synthetic trioctahedral 2:1 layer
lattice smectite-type minerals in which the central octahedral
layer contains one or more divalent metals having an ionic radius
not greater than 0.75 A as described hereinafter.
Representative metallic cations which are useful in this invention
may be derived from the following metals, the Pauling
electronegativity of which is given in parentheses (see "The Nature
of The Chemical Bond" L. Pauling, 3rd Edition. 1960): Be (1.5), Mg
(1.2), Al (1.5), Ga (1.6), In (1.7), Cu (1.9), Ag (1.9), La (1.1),
Hf (1.3), Cr (1.6), Mo (1.8), Mn (1.5), Fe (1.8), Ru (2.2), Os
(2.2), Co (1.8), Rh (2.2), Ir (2.2), Ni (1.8), Pd (2.2), Pt (2.2),
and Ce (1.1). Preferred metallic cations are Al.sup.3.sup.+,
In.sup.3.sup.+, Cr.sup.3.sup.+, and the rare earth cations,
particularly La.sup.3.sup.+ and Ce.sup.3.sup.+. Mixtures of two or
more metallic cations having a Pauling electronegativity greater
than 1.0 may be present in the catalyst in cation exchange
positions on the surface of the hectorite-type mineral.
Representative synthetic trioctahedral 2:1 layer-lattice
smectite-type minerals which are useful in this invention are the
structural analogs of hectorite in which the central octahedral
layer contains one or more divalent metals having an ionic radius
not greater than 0.75 A, provided that the metal is less than 95
mole % Mg, preferably less than 90 mole % Mg.
The charge-balancing cations of the hectorite-type minerals which
can be used to prepare the catalysts of the present invention must
be cations capable of being exchanged, preferably Na.sup.+,
Li.sup.+, or NH.sub.4.sup.+, unless they are metallic cations which
have a Pauling electro-negativity greater than 1.0.
The hectorite-type minerals useful in this invention can be
synthesized hydrothermally. In general a gel containing the
required molar ratios of the oxides or hydroxides of the metals
desired to be incorporated into the central octahedral layer,
silica, the charge balancing cations, and fluoride and having a pH
of at least 8 is hydrothermally treated at a temperature within the
range from 100.degree.C - 325.degree.C, preferably 250.degree.C -
300.degree.C, and preferably at the autogenous water vapor pressure
for a period of time sufficient to crystallize the desired
hectorite, generally 12 - 72 hours depending on the temperature of
reaction. In general as the reaction temperature decreases the
reaction time increases for well crystallized hectorite-type
minerals. The hectorite-type minerals can be crystallized from
melts of the oxides at very high temperatures, generally greater
than 950.degree.C. In these processes the charge balancing cation
must be too large to be incorporated into the layer lattices,
generally greater than 0.75 A, except that the charge balancing
cation may be Li.sup.+. Preferably the charge balancing cation is
Na.sup.+ or NH.sub.4 .sup.+ since these are readily removed by
cation exchange and replaced with the metallic cation as required
in the present inventive process and catalyst.
Hectorite-type clays can be represented by the structural
formula:
where the cations in the parentheses are the cations present in the
central octahedral layer, the two outer tetrahedral layers contain
the Si cations, and R represents the charge-balancing cations
exterior to the layer lattice of valence z. In the preferred
catalysts of the present invention:
M is divalent cation selected from the group consisting of Mg, Ni,
Co, Zn, Mn, Cu, and mixtures thereof, provided that M is less than
95 mole percent Mg(Mg<0.95(6-x)); R is at least one metallic
cation which has a Pauling electronegativity greater than 1.0;
and
More preferably 0 .ltoreq. y .ltoreq. 2 and M is selected from the
group consisting of Mg, Ni, Co, and mixtures thereof.
The hectorite-type clays can contain minor amounts of other metals
substituted isomorphously in the layer-lattices for the metals
indicated in the above formulas, such as Fe.sup.2.sup.+ and
Al.sup.3.sup.+ in the octahedral layer and Al.sup.3.sup.+, and
Ge.sup.4.sup.+ in the tetrahedral layers. Metals having an ionic
radius not greater than 0.75 A can be present in the octahedral
layer. Metals having an ionic radius not greater than 0.64 A can be
present in the tetrahedral layers. Generally the sum of such
extraneous isomorphously substituted metals will amount to no more
than 10 mole percent based on the metals present in the layer in
which the substitution occurs.
The catalyst of the present invention can be prepared by any
ion-exchange process wherein a metallic cation having a Pauling
electro-negativity greater than 1.0 can be made to replace the
exchangeable cation of the hectorite-type clay. Preferably an
aqueous solution of a soluble salt of the desired metallic cation
is admixed with the desired hectorite-type clay for a period of
time sufficient to effect the desired exchange. Preferably an
amount of metallic cation will be used which is from 100% to 500%
of the exchange capacity of the hectorite-type clay, more
preferably 100% to 300%. It is preferred to exchange at least 50%
of the exchangeable cations of the clay with the metallic cations
of this invention. It is also preferred to remove excess metallic
cation salt and the soluble salt by-products of the exchange from
the catlyst such as by filtration and washing prior to drying the
catalyst. Alternatively the excess metallic cation salt and soluble
salt by-product can be removed from the dried catalyst by slurrying
the catalyst in an appropriate solvent, such as water or methanol,
followed by filtration and re-drying. The exchange can also be
conducted using a solution of the metallic cation salt in an
appropriate organic solvents, such as methanol. Alternatively, the
process disclosed in U.S. Pat. No. 3,725,528 can be used to prepare
the catalyst.
The catalyst of this invention has been found to be active in
catalyzing the reaction between alkylatable aromatic hydrocarbons
and olefin-acting compounds under anhydrous alkylating conditions
in the liquid phase.
Alkylatable aromatic hydrocarbons which can be used in the
inventive process include benzene, toluene, xylene, the naphthalene
series of hydrocarbons, etc. Any aromatic hydrocarbon can be
alkylated if it has an unsubstituted carbon as long as steric
hindrance does not prevent alkylation with the particular
olefin-acting compound chosen for use in the process, and as long
as the alkyl side chains on the aromatic ring do not prevent the
aromatic compound from being adsorbed onto the layer-lattice
surfaces of the catalyst. Benzene is the preferred aromatic
hydrocarbon.
The olefin-acting compounds may be selected from the group
consisting of mono-olefins, alkyl bromides, alkyl chlorides, and
mixtures thereof. Representative olefins include ethylene,
propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene,
propylene tetramer, 1-octadecene, etc. Representative alkyl halides
include n-butyl bromide, n-butyl chloride, n-dodecyl bromide,
n-dodecyl chloride, etc.
The process is carried out in the liquid phase utilizing a
catalytically effective amount of the catalyst hereinbefore
described. The catalyst can be used in amounts from 1% to 100% by
weight based on the olefin-acting compound depending on the
particular metallic cation-exchanged hectorite-type catalyst chosen
for the reaction, the temperature of the reaction, and the length
of time the catalyst has been in service. Preferably a
concentration of catalyst from 2% to 50% by weight is used since
this gives a relatively fast alkylation, still more preferably 2%
to 10%.
The pressure can be elevated and is not critical as long as some of
the olefin-acting compound can be kept dissolved in the liquid
aromatic phase. Thus the pressure should be correlated with the
temperature at which the reaction is being carried out in order to
maintain the aromatic hydrocarbon in the liquid phase and to
maintain a sufficient amount of olefin-acting compound dissolved
therein to allow the alkylation reaction to proceed. Atmospheric
pressure is preferred because of the simplicity of operations under
atmospheric conditions.
The process is conducted at an elevated temperature since the rate
of alkylation is undesirably low at room temperature. Preferably
the temperature is in the range from 40.degree.C to 200.degree.C,
more preferably 70.degree.C to 150.degree.C. It is desirable to
conduct the process at the boiling point (reflux temperature) of
the alkylatable aromatic hydrocarbon provided that it is in the
above noted range. A non-alkylatable solvent, such as cyclohexane,
can be used to provide the liquid alkylating medium and the
temperature can conveniently be maintained at the boiling point of
the solvent.
The molar ratio of alkylatable aromatic hydrocarbon to alkylating
agent, i.e., the olefin-acting compound, can vary widely depending
on the product desired. Thus at higher ratios such as 10 or above
essentially only mono-alkylated product is obtained whereas at
lower ratios the amount of polyalkylated product is increased.
Preferably a molar ratio within the range from 3:1 to 20:1 will be
used, more preferably 5:1 to 10:1.
It is important to maintain the reaction system free of water since
water has a deactivating effect on the catalyst. Thus the catalyst
must be dried before use. This may conveniently be done by removing
the water from the catalyst at a low temperature, i.e., less than
about 200.degree.C. Alternatively the water may be removed by
azeotropic distillation from a mixture of the catalyst in the
alkylatable aromatic hydrocarbon or the solvent to be used in the
reaction. This method will also remove any water in these organic
systems and is preferred. The term "anhydrous" as used in this
specification and in the claims is intended to mean that any free
water which is present in the catalyst or the organic components
present in the reaction mix is removed from the reaction
system.
The following non-limiting examples are given in order to
illustrate the invention.
EXAMPLES 1 - 27
Various cation exchanged forms of the natural mineral hectorite
were prepared as follows: The exchange cation salt was dissolved in
500 to 750 ml. of methanol. Hectorite clay which had been
previously dispersed in water, centrifuged, and spray dried in
order to obtain the purified clay, was mixed in this salt solution
at a concentration of 300 milliequivalents of cation per 100 grams
of clay. This mixture was allowed to stand for approximately 20
hours before it was filtered. The filter cake was re-dispersed in
500 - 750 ml. of methanol followed by filtration for a total of
three successive washings. The cation exchanged hectorite was then
air dried for 20 hours at room temperature followed by oven drying
at 105.degree.C for 2 hours. The clay obtained by this process was
very fine and needed no grinding. In the case of
Ag.sup.+-hectorite, 10 ml. of concentrated nitric acid was added to
the methanol solution before adding the clay to the solution, in
order to prevent oxide formation of hydrolysis of the Ag.sup.+.
These cation exchanged hectorite clays were evaluated as catalysts
for the alkylation of benzene using the following procedure: 10
grams of the cation exchanged hectorite and 200 - 250 ml. of
benzene are refluxed in a round bottom flask equipped with a
Dean-Stark tube attached to remove, azeotropically, sorbed water
from the clay. After 2 - 4 hours the tube was removed and the
reflux condenser rinsed with methanol and air dried to remove any
residual moisture trapped in the condenser. 10 grams of the
alkylating agent were added to the flask and the mixture refluxed
with stirring for 24 hours. The clay was removed by filtration and
washed with 100 ml. of benzene. The benzene was removed from the
filtrate by vacuum evaporation leaving a product of unreacted
alkylating agent and/or alkylbenzene. This product was then weighed
and analyzed by either infrared spectrophotometry, refractometry,
or gas chromatography to determine the amount of alkyl-benzene
formed. The cation exchanged hectorites evaluated and the data
obtained are given in Table 1.
The data indicate that the natural hectorite clay containing
exchanged metallic cations having a Pauling electronegativity less
than or equal to 1.0 were ineffective as catalysts for the
alkylation of benzene. Metallic cations having a Pauling
electronegativity greater than 1.0 were effective catalysts when
exchanged onto hectorite. These include Be.sup.2.sup.+ and
Mg.sup.2.sup.+ (Group IIA), Al.sup.3.sup.+ and Im.sup.3.sup.+
(Group IIIA), La.sup.3.sup.+ (Group IIIB), Cr.sup.3.sup.+ (Group
VIA), Mn.sup.2.sup.+ (Group VIIB), Fe.sup.3.sup.+, Co.sup.2.sup.+,
Ni.sup.2.sup.+ and Pd.sup.2.sup.+ (Group VIII), Cu.sup.2.sup.+ and
Ag.sup.+ (Group IB), and Ce.sup.3.sup.+ (rare earths). The effect
of moisture within the reaction zone on the activity of certain of
the catalysts can be ascertained by reference to the data for
Examples 1, 4 and 6. The small amount of water which remained in
the reflux condenser (Examples 1,6) or in the atmosphere (Example
4) was sufficient to decrease the activity of Al.sup.3.sup.+
-exchanged hectorite approximately 50%, whereas In.sup. 3.sup.+
-exchanged hectorite was very active in the presence of such small
quantities of water.
TABLE 1 ______________________________________ Alkylation of
Benzene Alkylating Agent: Catalyst Weight Ratio = 1:1 Benzene:
Alkylating Agent Mole Ratio = 10:1 Temperature = 80.1.degree.C
(B.P. of Benzene) Duration of Reaction = 24 Hours Catalyst =
Various Cation Exchanged Forms of Hectorite Pauling % Exchangeable
Electro- Yields of Cation on negativity Alkylating Alkyl- Ex.
Hectorite of Cation Agent benzene
______________________________________ 1 Al.sup.3.sup.+ 1.5 n-Butyl
Bromide 80(36).sup.(a) 2 In.sup.3.sup.+ 1.7 n-Butyl Bromide 86 3
H.sup.+ 2.1 n-Butyl Bromide 10 4 Al.sup.3.sup.+ 1.5 n-Butyl
Chloride 18(40).sup.(b) 5 In.sup.3.sup.+ 1.7 n-Butyl Chloride 94 6
Al.sup.3.sup.+ 1.5 Lauryl Bromide 89(48).sup.(a) 7 Inhu 3.sup.+ 1.7
Lauryl Bromide (86).sup.(a) 8 Fe.sup.3.sup.+ 1.8 Lauryl Bromide
(31).sup.(a) 9 Al.sup.3.sup.+ 1.5 1-Octadecene 93.sup.(c) 10
In.sup.3.sup.+ 1.7 1-Octadecene 93.sup.(d) 11 Al.sup.3.sup.+ 1.5
1-Dodecene 88 12 Fe.sup.3.sup.+ 1.8 1-Dodecene 88 13 Cr.sup.3.sup.+
1.6 1-Dodecene 100 14 La.sup.3.sup.+ 1.1 1-Dodecene 100 15
Ce.sup.3.sup.+ 1.1 1-Dodecene 99 16 Be.sup. 2.sup.+ 1.5 1-Dodecene
96 17 Mg.sup.2.sup.+ 1.2 1-Dodecene 96 18 Mn.sup.2.sup.+ 1.5
1-Dodecene 92 19 Co.sup.2.sup.+ 1.8 1-Dodecene 91 20 Ni.sup.2.sup.+
1.8 1-Dodecene 93 21 Cu.sup.2.sup.+ 1.9 1-Dodecene 99 22
Pd.sup.2.sup.+ 2.2 1-Dodecene 71 23 Ag.sup.+ 1.9 1-Dodecene 100 24
Ca.sup.2.sup.+ 1.0 1-Dodecene 52 25 Ba.sup.2.sup.+ 0.9 1-Dodecene 5
26 Li.sup.+ 1.0 1-Dodecene 5 27 Na.sup.+ 0.9 1-Dodecene
Trace.sup.(e) ______________________________________ .sup.(a)
Methanol Rinse of Reflux Condenser Omitted .sup.(b) Nitrogen
Circulated through the Reaction Flask .sup.(c) Small Amount of
n-Butyl Bromide Added to Promote the Reaction .sup.(d) Small amount
of Lauryl Bromide added to promote the reaction .sup.(e) Clay
without Exchange Treatment - Primarily Na.sup.+ Form.
EXAMPLES 28 - 43
Several cation exchanged hectorites were prepared by at least one
of the following procedures as indicated in Table 2: Process A --
exchange in methanol solution as in Examples 1 - 27; Process B --
exchange in aqueous solution substituting water for methanol in
Process A except in the last washing step; Process C -- exchange in
aqueous solution, no washing. These catalysts were evaluated for
the alkylation of benzene by 1-dodecene at a 1-dodecene:catalyst
weight ratio of 10:1 using the same process as in Examples 1-27.
The percent conversion of the olefin after one hour is given in
Table 2. The catalysts used in Examples 33, 34, 37 and 38 were the
same catalysts used in Examples 32, 33, 36 and 37 respectfully,
after rinsing them with benzene.
The data indicate that water is the preferred solvent for the
metallic cation salt, i.e., for the exchange solution, and that the
catalyst should be washed to remove soluble salts from the
catalyst. The catalyst can be re-used after rinsing with benzene to
remove adsorbed products from the catalyst.
TABLE 2 ______________________________________ Alkylation of
Benzene with 1-Dodecene Benzene: 1-Dodecene Mole Ratio = 10:1
1-Dodecene: Catalyst Weight Ratio: = 10:1 Temperature =
80.1.degree.C (B.P. of Benzene) Duration of Run = One Hour
Exchangeable 1-Dodecene Catalyst % Cation on to Cation Preparation
Conversion Ex. Hectorite Ratio Process of Olefin
______________________________________ 28 Al.sup.3.sup.+ 1,000/1 A
53 29 Al.sup.3.sup.+ 1,000/1 B 95 30 Al.sup.3.sup.+ 1,000/1 C 1.2
31 Al.sup.3.sup.+ 1,000/1 C 4.4 32 Al.sup.3.sup.+ 1,000/1 B 97 33
Al.sup.3.sup.+ 1,000/1 B 77.sup.(a) 34 Al.sup.3.sup.+ 1,000/1 B
37.sup.(b) 35 Cr.sup.3.sup.+ 526/1 A 90 36 Cr.sup.3.sup.+ 526/1 B
99.sup.+ 37 Cr.sup.3.sup.+ 526/1 B 82.sup.(c) 38 Cr.sup.3.sup.+
526/1 B 58.sup.(d) 39 In.sup.3.sup.+ 263/1 A 3 40 In.sup.3.sup.+
263/1 B 99 41 Mg.sup.2.sup.+ 833/1 A 29 42 Fe.sup.3.sup.+ 357/1 B
84 43 Ag.sup.+ 256/1 A 21 ______________________________________
.sup.(a) The catalyst from the previous experiment, after X hours
reactio time and Y% conversion of dodecene, was re-used after it
was rinsed with benzene, where X = 4 hours and Y = 99.3%. .sup.(b)
As .sup.(a), except X = 7 hours and Y = 99.1% .sup.(c) As .sup.(a),
except X = 1 hours and Y = 99.sup.+% .sup.(d) As .sup.(a), except X
= 3 hours and Y = 93.4%
EXAMPLES 44 - 54
An Al.sup.3.sup.+ -exchanged hectorite and a Cr.sup.3.sup.+
-exchanged hectorite (purified natural clay as in Examples 1 - 27)
were prepared by the aqueous exchange process B of Examples 28 -
43. These clays were evaluated as catalysts for the alkylation of
benzene by 1-dodecene at various mole ratios of benzene to dodecene
and/or various weight ratios of dodecene to catalyst as indicated
in Table 3. The percent conversion of dodecene after 1 hour and, in
some cases, 24 hours using the same process as in Examples 1 - 27
was determined. The data obtained are given in Table 3.
The data indicate that these exchanged clays were excellent
catalysts at concentrations of exchanged clay greater than about
2%, based on the weight of dodecene, although concentrations as low
as 1% converted most of the dodecene in 24 hours.
Table 3 ______________________________________ Alkylation of
Benzene with 1-Dodecene Benzene: 1-dodecene Mole Ratio: as
indicated 1-dodecene:Catalyst Weight Ratio: as indicated
Temperature: 80.1.degree.C (B.P. of Benzene) Duration of Run: 1, 24
Hours Catalyst: Al.sup.3.sup.+ - and Cr.sup.3.sup.+ -exchanged
Hectorite as indicated Exchangeable 1-dodecene Benzene to %
Conversion Cation on to Catalyst 1-dodecene of 1-dodecene Ex.
Hectorite Wt. Ratio Mole Ratio 1 Hr. 24 Hr.
______________________________________ 44 Cr.sup.3.sup.+ 10:1 10:1
99.6 -- 45 Cr.sup.3.sup.+ 20:1 10:1 98.4 -- 46 Cr.sup.3.sup.+ 40:1
10:1 70:1 -- 47 Cr.sup.3.sup.+ 100:1 10:1 43.7 83.8 48
Al.sup.3.sup.+ 10:1 10:1 97.0 -- 49 Al.sup.3.sup.+ 20:1 10:1 98.2
-- 50 Al.sup.3.sup.+ 40:1 10:1 82.1 99.0 51 Al.sup.3.sup.+ 50:1 5:1
55.2 90.2 52 Al.sup.3.sup.+ 100:1 10:1 34.2 78.0 53 Al.sup.3.sup.+
100:1 5:1 18.9 71.6 54 Al.sup.3.sup.+ 100:1 20:1 29.6 67.1
______________________________________
EXAMPLE 55
A synthetic hectorite-type clay was prepared by reacting at a
temperature of 350.degree.C in a Ag-lined stainless steel autoclave
under the autogenous water vapor pressure created in the autoclave
for 48 hours a composition having the molar formula:
the product obtained, after drying at 105.degree.C, had x-ray
diffraction peaks at 12.5 A and 1.517 A which indicates that the
product was a well crystallized hectorite-type clay. The expected
formula for this nickleferous hectorite is:
This synthetic hectorite-type clay mineral was exchanged to the
Al.sup.3.sup.+ -form as follows: the dried clay was mixed into an
aqueous AlCl.sub. 3 solution at a concentration of 300
milliequivalents of Al.sup.3.sup.+ per 100.sup.3 grams of clay. The
mixture was allowed to stand for approximately 20 hours before it
was filtered. The filter cake was re-dispersed in 500-750 ml. of
deionized water followed by filtration for a total of two
successive washings. Thereafter another washing was undertaken
substituting methanol for the deionized water. The Al.sup.3.sup.+
-cation exchanged hectorite-type clay was then air dried for 20
hours at room temperature followed by oven drying at 105.degree.C
for 2 hours. The catalyst obtained by this process was very fine
and needed no grinding.
The Al.sup.3.sup.+ -exchanged synthetic hectorite-type clay was
evaluated as follows: 1 gram of the clay and 200-500 ml. of benzene
were refluxed in a round bottom flask equipped with a Dean-Stark
tube attached to remove, azeotropically, sorbed water from the
clay. After 2-4 hours the tube was removed and the reflux condenser
rinsed with methanol and air dried to remove any residual moisture
trapped in the condenser. 10 grams of 1-dodecene were then added to
the flask and the mixture refluxed with stirring.
After 1 hour a sample was taken and analyzed by gas chromatographic
analysis. 21.1% of the 1-dodecene was converted to dodecylbenzene
and 9.8% of the 1-dodecene was converted to heavy alkylate. After
24 hours another sample was taken and analyzed. 67.5% of the
1-dodecene was converted to dodecyclbenzene and 15.8% of the
1-dodecene was converted to heavy alkylate.
EXAMPLE 56
A synthetic hectorite-type clay was prepared by the process of
Example 55 starting with a composition having the molar
formula:
the product obtained, after drying at 105.degree.C, had x-ray
diffraction peaks at 12.7 A and 1.522 A which indicates that the
product was a well crystallized hectorite-type clay. The expected
formula for this cobaltiferous hectorite is:
This synthetic hectorite-type clay was exchanged to the
Al.sup.3.sup.+ -form and evaluated as in Example 55. 48.1% of the
1-dodecene was converted to dodecyclbenzene and 8.7% of the
1-dodecene was converted to heavy alkylate after 24 hours
refluxing.
EXAMPLE 57
The procedures of Example 55 are repeated wherein the
hectorite-type clay is exchanged with the following metallic
cations: Cr.sup.3.sup.+, In.sup.3.sup.+, Fe.sup.3.sup.+,
Ga.sup.3.sup.+, Mn.sup.2.sup.+, Co.sup.3.sup.+, Co.sup.2.sup.+,
Ni.sup.2.sup.+, Cu.sup.2.sup.+, Ag.sup.+, Be.sup.2.sup.+,
Mg.sup.2.sup.+, La.sup.3.sup.+, Ce.sup.3.sup.+, Pd.sup.2.sup.+,
Pt.sup.2.sup.+, and mixtures thereof.
Thus these catalysts have the following structural formula:
where R.sup.z = Cr.sup.3.sup.+, In.sup.3.sup.+, Fe.sup.3.sup.+,
Ga.sup.3.sup.+, Mn.sup.2.sup.+, Co.sup.3.sup.+, Co.sup.2.sup.+,
Ni.sup.2.sup.+, Cu.sup.2.sup.+, Ag.sup.+, Be.sup.2.sup.+,
Mg.sup.2.sup.+, La.sup.3.sup.+, Ce.sup.3.sup.+, Pd.sup.2.sup.+,
Pt.sup.2.sup.+, and mixtures thereof.
EXAMPLE 58
The procedures of Example 55 are repeated wherein the autoclave
feed composition has the molar formula:
the formula for this nickeliferous-cobaltiferous hectorite-type
clay is:
The formula for the Al.sup.3.sup.+ -exchanged catalyst is:
It will be understood that while I have explained the invention
with the aid of specific examples, nevertheless considerable
variation is possible in choice of raw materials, proportions,
processing conditions, and the like, within the broad scope of the
invention as set forth in the claims which follow. Thus, for
example, my inventive catalyst may be used simultaneously with
other catalytic materials so as to suit particular conditions and
circumstances.
* * * * *